An
efficient
electrochemical
bromocyclization
of
allenols
has
been
realized
for
the
synthesis
spirocyclic
2,5-dihydrofurans.
The
reaction
used
commercially
available
and
nontoxic
KBr
as
brominating
source
in
a
simple
setup
under
open-air
conditions.
Notably,
optically
active
products
can
be
obtained
from
2,3-allenols
without
any
racemization,
further
enhancing
synthetic
utility.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(36), С. 16252 - 16261
Опубликована: Авг. 31, 2022
Chiral
iridium
complexes
derived
from
Crabtree's
catalyst
are
highly
useful
in
modern
hydrogenations
of
olefins
attributed
to
high
reactivity,
stereoselectivity,
and
stability.
Despite
that
these
precatalysts
pH
neutral,
the
reaction
mixtures
turn
acidic
under
hydrogenation
conditions.
This
Perspective
is
devoted
implications
intrinsic
Brønsted
acidity
catalytic
intermediates
asymmetric
olefins.
has
often
been
used
only
as
a
rationale
for
side-product
formation,
more
recent
methodologies
have
started
use
this
property
advantageously.
We
hope
serves
stimulant
development
such
compelling
new
hydrogenations.
The
inherent
scientific
opportunities
utilizing
or
annihilating
generated
acid
enormous,
potential
innovations
outlined
toward
end.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(28)
Опубликована: Май 11, 2023
Catalytic
asymmetric
hydrogenation
of
enamido
phosphorus
derivatives
is
one
the
most
efficient
methods
for
construction
chiral
amino
products,
among
which
congested
tetra-substituted
substrates
remains
an
unaddressed
challenge.
In
this
study,
we
utilize
a
commercially
available
Rh-Josiphos
system
and
stereoselective
wide
set
cyclic
β-enamido
phosphonates/phosphine
oxides,
thus
enabling
access
to
β-amino
compounds
featuring
two
vicinal
stereocenters.
This
protocol
was
broadly
applicable
different
ring
systems
possessing
various
phosphonate/phosphine
oxide
groups
further
applied
in
preparation
amino-phosphine
ligands.
DFT
mechanistic
explorations
indicate
that
C=C
migratory
insertion
into
RhIII
-H
bond
could
be
rate-
stereo-determining
step.
The
origins
stereoselectivity
are
revealed
through
distortion/interaction
analysis,
primarily
regulated
by
distinguished
dispersion
interactions
steric
repulsions.
Patai's chemistry of functional groups,
Год журнала:
2025,
Номер
unknown, С. 1 - 26
Опубликована: Фев. 26, 2025
Abstract
The
development
of
highly
efficient
catalysts
for
alkene
hydrogenation
has
continuously
received
great
attention,
both
from
academia
and
industry.
Cobalt‐based
homogeneous
have
emerged
as
attractive
alternatives
to
“traditional”
precious‐metal
in
hydrogenation,
owing
the
unique
properties
outstanding
catalytic
performance
addition
benefits
low
cost
environmentally
benign
nature.
In
this
chapter,
advances
cobalt‐catalyzed
are
summarized
provide
a
comprehensive
overview
cobalt
catalysts,
their
behavior,
reaction
mechanisms.
An
efficient
electrochemical
bromocyclization
of
allenols
has
been
realized
for
the
synthesis
spirocyclic
2,5-dihydrofurans.
The
reaction
used
commercially
available
and
nontoxic
KBr
as
brominating
source
in
a
simple
setup
under
open-air
conditions.
Notably,
optically
active
products
can
be
obtained
from
2,3-allenols
without
any
racemization,
further
enhancing
synthetic
utility.